An investigation of soil quality parameters relating to agricultural reuse and land disposal options for the management of biosolids

Sludge provides valuable nutrients to soil. Application of sludge to land is subject to a number of limitations. Its use as a soil conditioner represents a "beneficial reuse option". Primary and secondary sludge from Dublin city is treated in Ringsend treatment plant where it undergoes thermal drying. This study investigates the feasibility of land application of thermally dried biosolids (TDB) from Ringsend treatment plant.

An evaluation of septic tank effluent movement in soil and groundwater systems

Recent studies have shown that septic tank systems are a major source of groundwater pollution. Many public health workers feel that the most cri^cal aspect of the use of septic tanks as a means of sewage disposal is the contamination of private water wells with attendant human health hazards. In this study the movement and attenuation of septic tank effluents in a range of soil/overburden types and hydrogeological situations was investigated. The suitability of a number of chemical and biological tracer materials to monitor the movement of septic tank effluent constituents to groundwater sources was also examined. The investigation was divided into three separate but inteiTelated sections. In the first section of the study the movement of septic tank effluent from two soil treatment systems was investigated by direct measurements of soil nutrient concentrations and enteric bacterial numbers in the soil beneath and downgradient of the test systems. Two sites with different soil types and hydrogeological characteristics were used. The results indicated that the attenuation of the effluent in both of the treatment systems was incomplete. Migration of nitrate, ammonium, phosphate and fecal bacteria to a depth of 50 cm beneath the inverts of the distribution tiles was demonstrated on all sampling occasions. The lateral migration of the pollutants was less pronounced, although on occasions high nutrients levels and fecal bacterial numbers were detected at a lateral distance of 4.0 m downgradient of the test systems. There was evidence that the degree and extent of effluent migration was increased after periods of heavy or prolonged rainfall when the attenuating properties of the treatment systems were reduced as a result of saturation of the soil. The second part of the study examined the contamination of groundwaters downgradient of septic tank soil treatment systems. Three test sites were used in the investigation. The sites were chosen because of differences in the thicknesses and nature of the unsaturated zone available for effluent attenuation at each of the locations. A series of groundwater monitoring boreholes were installed downgradient of the test systems at each of the sites and these were sampled regularly to assess the efficiency of the overburden material in reducing the polluting potential of the wastewater. Effluent attenuation in the septic tank treatment systems was shown to be incomplete, resulting in chemical and microbiological contamination of the groundwaters downgradient of the systems. The nature and severity of groundwater contamination was dependent on the composition and thickness of the unsaturated zone and the extent of weathering in the underlying saturated bedrock. The movement of septic tank effluent through soil/overburdens to groundwater sources was investigated by adding a range of chemical and biological tracer materials to the three septic tank systems used in section two of the study. The results demonstrated that a single tracer type cannot be used to accurately monitor the movement of all effluent constituents through soils to groundwater. The combined use of lithium bromide and endospores of Bacillus globigii was found to give an accurate indication of the movement of both the chemical and biological effluent constituents.

Transfer of radionuclides from soil to vegetation in selected Irish ecosystems

This thesis details the findings of a study relating the transfer of 238U, 228Ra (232Th), 226Ra, and 137Cs from soil to vegetation in an Atlantic blanket bog, upland blanket bog and semi-natural grassland situated along the north-west coast of Ireland. The results of this study provide information on the uptake of these radionuclides by the indigenous vegetation found present in these ecosystems. The ecosystems chosen are internationally recognizable ecosystems and provide a wide variety of vegetation species and contrasting soil physiochemical properties which allow the influence of these parameters on radionuclide uptake to be assessed. The levels of radionuclides in the soil and vegetation were measured using gamma spectrometry, alpha spectrometry and ICP-MS. The nutrient status of the vegetation and soil physiochemical properties were measured using atomic absorption, flame photometry and other analytical techniques. The results of the study indicate that the uptake of 238U and 228Ra (232Th) by vegetation from all three ecosystems was negligible as the levels in all vegetation was below the limits of detection for the methods used in this study. These results appear to indicate that the vegetation studied do not possess the ability to accumulate significant levels of these radionuclides however this assumption cannot be upheld in the case of the Atlantic blanket bog as the levels in the soil of this ecosystem were too low for detection. Similar results were obtained for 226Ra uptake in both the Atlantic blanket bog and grassland for all vegetation with the exception of H. lanatus from the grassland ecosystem. Radium-226 uptake in upland blanket bog was higher and was detectable in the majority of vegetation indigenous to this ecosystem. Transfer factor values ranged from 0.07 to 2.35 and the TF values for E. tetralix were significantly higher than all other vegetation studied. This species of heather demonstrated the ability to accumulate 226Ra to a greater extent than all other vegetation. The uptake of 226Ra by upland blanket bog vegetation appears to be significantly influenced by a range of soil physiochemical properties. The nutrient status of the vegetation, in particular the calcium content in the vegetation appears to have a negative impact on the uptake of this radionuclide. Potassium-40 was detectable in all vegetation present in the three ecosystems and the levels in the grassland soil were significantly higher than the levels in both bogland soils. Transfer factor values for Atlantic blanket bog vegetation ranged from 0.9 to 13 .8 and were significantly higher in E. vaginatum in comparison to C. vulgaris. Potassium-40 TF values for upland blanket bog vegetation on average ranged from 1.4 for C. vulgaris (stems) to 5.2 for E. vaginatum and were statistically similar for all species of vegetation. Transfer factor values for grassland vegetation ranged from 0.7 to 3.8 and were also statistically similar for all species of vegetation indicating that the transfer of 40K to vegetation within the upland bog and grassland ecosystem is not dependent on plant species. Comparisons of 40K TF values for all three ecosystems indicate that the uptake in E. vaginatum from the Atlantic blanket bog was statistically higher than all other vegetation studied. This appears to indicate that E. vaginatum has the ability to accumulate 40K, however, this species of vegetation was also present in the upland blanket and did not demonstrate the same behaviour. The uptake of 40K by vegetation from all three ecosystems was significantly affected by a range of soil physiochemical properties and in some cases the results were contradictory in nature possibly indicating that the affect of these parameters on 40K uptake is species dependent. The most obvious trend in the data was the influence of soil CEC and magnesium levels in vegetation on 40K TF values. A positive correlation was apparent between the CEC of the soil and 40K uptake in vegetation from both the Atlantic blanket bog and grassland ecosystem. A similar trend was apparent between magnesium levels in vegetation and 40K TF values for the upland blanket bog and grassland vegetation. Caesium-13 7 levels were found to be significantly higher in the two bogland soils in comparison to the grassland soil and levels of 137Cs decreased with increasing soil depth. Transfer factor values for Atlantic blanket bog vegetation ranged from 1.9 to 9.6 and TF values were significantly higher in the leaves o f C. vulgaris in comparison to all other vegetation from this ecosystem. Caesium-13 7 TF values for the upland blanket bog vegetation on average ranged from 0.29 for E. tetralix to 1.6 for C. vulgaris. Uptake by the leaves of C. vulgaris was significantly higher than all other vegetation present thereby supporting the trend found within the Atlantic blanket bog vegetation. These results appear to indicate that the leaves of C. vulgaris have the ability to accumulate significant quantities of 137Cs and also that the uptake of 137Cs by this vegetation is dependent on plant compartment as the stems of this vegetation contained significantly lower levels than the leaves in both ecosystems. The uptake of 137Cs by grassland vegetation was very low and was only detectable in a fraction of the vegetation sampled. Caesium-137 TF values for grassland vegetation were in general lower than 0.02. The impact of soil physiochemical properties and nutrient status of vegetation on 137Cs uptake by vegetation appears to be complex and in some cases contradictory. The most apparent trend in the data was the positive influence of vegetation nutrients on 137Cs uptake in particular the magnesium levels present in the vegetation and to a lesser extent the calcium levels present. The results in general indicate that the uptake of 226Ra, 40K and 137Cs by the chosen vegetation is varied and complex and is significantly dependent on the species of vegetation, soil radionuclide concentration, soil physiochemical properties and the nutrient status of the vegetation.

The spatial analysis and speciation of uranium and thorium series radionuclides in the soil of the Cronamuck Valley, County Donegal, Ireland

This thesis details the findings of a study into the spatial distribution and speciation of 238U, 226Ra and 228Ra in the soils of the Cronamuck valley, County Donegal . The region lies on the north-eastern edge of the Barnesmore granite and has been the subject of uranium prospecting efforts in the past. The results of the project provide information on the practicability of geostatistical techniques as a means of estimating the spatial distribution of natural radionuclides and provide insight into the behaviour of these nuclides and their modes of occurrence and enrichment in an upland bog environment. The results of the geostatistical survey conducted on the area indicate that the primary control over the levels of the studied nuclides in the soil of the valley is the underlying geology. Isopleth maps of nuclide levels in the valley indicate a predominance of elevated nuclide levels in the samples drawn from the granite region, statistical analysis of the data indicating that levels of the nuclides in samples drawn from the granite are greater than levels drawn from the non-granite region by up to a factor of 4.6 for 238U and 4.9 for 226Ra. Redistribution of the nuclides occurs via drainage systems within the valley, this process being responsible for transport of nuclides away from the granite region resulting in enrichment of nuclides in soils not underlain by the granite. Distribution of the nuclides within the valley is erratic, the effect of drainage f lows on the nuclides resulting in localized enriched areas within the valley. Speciation of the nuclides within one of the enriched areas encountered in the study indicates that enrichment is as a result of saturation of the soil with drainage water containing trace amounts of radionuclides. 238U is primarily held within the labile fractions (exchangeable cat ions + easily oxidisable organics + amorphous iron oxides ) of the soil , 226Ra being associated with the non- labile fractions, most probably the resistant organic material. 228Ra displays a significant occurrence in both the labile and non- labile fractions. The ability of the soil to retain uranium appears to be affected largely by the redox status of the soil, samples drawn from oxidizing environments tending to have little or no uranium in the easily oxidisable and amorphous iron oxide fractions. This loss of uranium from oxidised soil samples is responsible for the elevated 226Ra /238U disequilibrium encountered in the enriched areas of the valley. Analysis of the data indicates that samples displaying elevated 226Ra/238U ratios also exhibit elevated 228Ra/238U ratios indicating a loss of uranium from the samples as opposed to an enrichment of 226Ra.

Development of sensing systems for environmental monitoring

This project focused on the investigation and the development of a chemical sensing system for the determination of chromium Cr6+ and a bio-reactor followed by electrochemical detection at a glassy carbon electrode, for the determination of organochlorine compounds. The conjugation of Cr6+ with 1,5-diphenylcarbazide was studied at various types of electrodes such as glassy carbon, ultra-trace epoxy-graphite, chemically or un-modified carbon-paste and dropping-mercury. The cyclic voltammetric behaviour of the complex was also investigated. In addition, the possibility of developing a chemical sensor, Le. an electrochemical probe capable of sensing Cr6+ through its complexation with 1,5-diphenylacarbazide was studied. The conjugations of l-chloro-2,4-dinitrobenzene, 2,4-dichloronitrobenzene and ethacrynic, which are electrophilic organochlorine compounds, with reduced glutathione, were studied in order to test the bioreactor developed, based on the immobilisation of glutathione s-transferase. This was carried out at different types of electrodes such as glassy-carbon, gold, silver, platinum, epoxy-graphite, hangingmercury, and ferrocene-modified rotating-disc electrodes.